The present invention relates to a primary cell, comprising an alkali metal as the active electrode material, in particular as the active anode material, and an electrolyte comprising a boron compound, wherein the boron compound is compound according to formula (1), (2), (3), (4), (7) or (8):
Legal claims defining the scope of protection, as filed with the USPTO.
. The lithium primary cell battery according to, wherein each of R1, R2, R3, R4 and R5 independent from one another is unsubstituted or is monosubstituted or multiple substituted with at least one substituent selected from the group consisting of: alkyl, fluoroalkyl, alkoxy, carbonyl, carboxyl, thiol, thio alkoxide, aryl, ether, thioether, excluding thiophene, nitro, cyano, amino, azido, amidino, hydrazino, hydrazono, carbamoyl, sulfo, sulfamoyl, sulfonylamino, alkylaminosulfonyl, alkylsulfonylamino and/or halogens, wherein R1, R2, R3, R4 or R5 is not thiophene.
. The lithium primary cell battery according to, wherein the boron compound is:
. The lithium primary cell battery according to, wherein the boron compound is:
. The lithium primary cell battery according to, wherein the boron compound is present in the electrolyte in a concentration in the range of 0.001 mol*lto 0.5 mol*l.
. The lithium primary cell battery according to, wherein the electrolyte is a non-aqueous electrolyte.
. The lithium primary cell battery according to, wherein the non-aqueous electrolyte:
. The lithium primary cell battery according to, wherein the electrolyte comprises an anhydrous alkali salt comprising LiClO, LiPF, LiBF, LiAsF, LiSbF, LiClO, LiAlCl, LiGaCl, LiC(SOCF), LiN(SOCF), LiSCN, LiOSCFCF, LiCFSO, LiOCF, LiSOF, LiB(CH), LiCFSOor mixtures thereof.
. Use of a boron compound as an electrolyte additive of the lithium primary cell battery according to, wherein each of R1, R2, R3, R4 and R5 independent from one another is unsubstituted or is monosubstituted or multiple substituted with at least one substituent selected from the group consisting of: alkyl, fluoroalkyl, alkoxy, carbonyl, carboxyl, thiol, thio alkoxide, aromatic compound, ether, thioether, nitro, cyano, amino, azido, amidino, hydrazino, hydrazono, carbamoyl, sulfo, sulfamoyl, sulfonylamino, alkylaminosulfonyl, alkylsulfonylamino and/or halogens, wherein R1, R2, R3, R4 or R5 is not thiophene.
. Use of a boron compound as an electrolyte additive of the lithium primary cell battery according to, wherein the boron compound is:
. Use of a boron compound as an electrolyte additive of a lithium primary cell battery according to, wherein the boron compound is:
Complete technical specification and implementation details from the patent document.
This application is the United States National Phase under 35 U.S.C. § 371 of PCT International Patent Application No. PCT/EP2020/068552, filed on Jul. 1, 2020, which claims the benefit of European Patent Application No. 19185488.4, filed on Jul. 10, 2019, the disclosures of which are hereby incorporated by reference herein in their entireties.
The present invention relates to boron-based electrolyte additives for a primary alkali metal electrochemical cell and to a corresponding primary alkali metal electrochemical cell.
A monotonic pulse shape is generally desirable in electrochemical cells. A monotonic pulse shape exists when the voltage curve remains constant under pulse conditions or decreases to the minimum at the end of the pulse, and the minimum voltage of the first pulse in a pulse series is higher than the minimum voltage of the last pulse. The voltage curve of this pulse series is usually rectangular ().
Voltage delay is an undesirable characteristic in the discharge profile of implantable alkali metal cells under current pulse discharge conditions. Voltage delay is caused by the formation of relatively high impedance cover layers on the anode surface, resulting in an increase in the internal resistance of the battery. This effect can only be observed when the batteries are subjected to high pulse current densities and, in the process, the battery voltage drops disproportionately, that is, the voltage at the beginning of the first pulse is lower than at the end of the pulse or when the first pulse is lower than the minimum voltage of the last pulse ().
Voltage delay normally first becomes apparent under pulse loading in alkali metal/metal oxide and alkali metal/mixed metal oxide cells at more than 40% DoD (depth of discharge) of their capacity discharge or after extended storage. In certain instances, a high impedance cover layer forms on the anode surface, for example due to dissolution of the cathode active material or due to discharge products in the battery electrolyte, which under certain pulse discharge conditions can result in voltage delay or in non-monotonic behavior.
Electrolyte additives such as phosphates, dicarbonates, nitrites, alkyl phosphates and organic additives including hydroxyl groups (—OH) and carboxyl groups for suppressing or reducing the voltage delay for alkali metal/transition metal oxide (such as Li/SVO) and alkali metal/mixed oxides x and/or transition metal oxide or for Li/SVO cells are known in the prior art.
The aforementioned additives are typically used for alkali metal/transition metal oxide systems, in particular for lithium/silver vanadium oxide (Li/SVO) and lithium/silver vanadium oxide hybrid cathodes (Li/SVO hybrid cathodes), in which increases in impedance and, consequently, voltage delay occur due to high impedance cover layers made of metal deposits such as vanadium, silver and/or metal alloys on the electrode surface. The aforementioned additives, however, are not suitable for alkali metal/carbon monofluoride (Li/CFx) systems, in which the voltage delay occurs due to fluoride lithium deposits on the anode surface.
Organoborate salts are also known in the prior art (for example from U.S. Pat. No. 7,740,986 B2) as an electrolyte conducting salt or an electrolyte additive for lowering self-discharge and for reducing/eliminating the voltage delay after storage at room and elevated temperatures of the Li/CFx cells. However, compared to the standard electrolyte, the organoborate-based electrolytes show increased battery resistance (see Example 01).
Based on this background, it is an objective of the present invention to provide an electrolyte additive for primary cells, especially containing lithium as the active electrode material, which reduces, and preferably eliminates, voltage delay and reduces battery impedance.
The present disclosure is directed toward overcoming one or more of the above-mentioned problems, though not necessarily limited to embodiments that do.
At least the object is achieved by a primary cell having the features of claimand by the use of a boron compound having the features of claim. Suitable embodiments are provided in the corresponding dependent claims and in the following description.
According to claim, a primary cell is provided, which comprises alkali metal as the active electrode material, particularly as the active anode material, and an electrolyte comprising a boron compound, in particular an organic boron compound.
The term “primary cell” is used in its generally known, technical meaning in the context of the present description. It denotes in particular a galvanic cell that, once discharged, can no longer be electrically charged. Primary cells are also referred to as primary battery at times.
The boron compound is in particular a non-ionic compound, that is, preferably not a salt of a boron-containing acid.
According to the present invention, it is particularly provided that the boron compound is a compound according to formula (1), (2), (3), (4), (7) or (8):
where R1, R2, R3, R4 and R5 independent from one another are selected from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl, thioether, heterocyclic compounds, aryl and heteroaryl, wherein R1, R2, R3, R4 or R5 is not thiophene.
In one embodiment of the primary cell according to the present invention, it is provided that R1, R2, R3, R4 and R5 independent from one another are unsubstituted or are monosubstituted or multiple substituted with at least one substituent selected from the group consisting of: alkyl, fluoroalkyl, alkoxy, carbonyl, carboxyl, thiol, thio alkoxide, aryl, ether, thioether, nitro, cyano, amino, azido, amidino, hydrazino, hydrazono, carbamoyl, sulfo, sulfamoyl, sulfonylamino, alkylaminosulfonyl, alkyl sulfonyl amino and/or halogen. Preferred substituents comprise halogens, fluoroalkyls and cyano or nitrile groups, wherein R1, R2, R3, R4 or R5 is not thiophene.
In one embodiment of the primary cell according to the present invention, it is provided that the boron compound is a compound according to formula (1), where R1 is an alkyl, in particular a Cto Calkyl, in particular methyl, cyclopropyl or cyclohexyl, or an aryl, in particular a phenyl, a benzyl or a naphthyl, which is unsubstituted or substituted with one or more Cto Calkyl, —F, —Cl, —Br, —I, —CN, —CFor —OCF, and each of R2 to R4 and R5 independent from one another is a CCalkyl.
In one embodiment of the primary cell according to the present invention, it is provided that the compound according to formula (1) is:
In one embodiment of the primary cell according to the present invention, it is provided that the boron compound is a compound according to formula (2), where each of R1 to R4 and R5 independentl from one another is a Cto Calkyl.
In one embodiment of the primary cell according to the present invention, it is provided that the compound according to formula (2) is:
In one embodiment of the primary cell according to the present invention, it is provided that the boron compound is a compound according to formula (3), where R1 is an alkyl, an alkenyl, in particular an allyl or an aryl, in particular a benzyl, phenyl, or benzoate, which is unsubstituted, or substituted with one or more Cto Calkyl, —F, —Cl, —Br, —I, —CN, —CFor —OCFor a compound according to formula (3), and each of R2 and R3 independent is a Cto Calkyl.
In one embodiment of the primary cell according to the present invention, it is provided that the compound according to formula (3) is:
In one embodiment of the primary cell according to the present invention, it is provided that the boron compound is a compound according to formula (4), where each of R1, R2 and R3 independent from one another is a Cto Calkyl.
In one embodiment of the primary cell according to the present invention, it is provided that the compound according to formula (4) is:
In one embodiment of the primary cell according to the present invention, it is provided that the boron compound is a compound according to formula (7), where each of R1 to R3 independent from one another is an alkyl, in particular a Cto Calkyl, in particular methyl, or an aryl, in particular a phenyl, which is unsubstituted or substituted with one or more —F, —Cl, —Br, —I, —CN, —CFor —OCF.
In one embodiment of the primary cell according to the present invention, it is provided that the compound according to formula (7) is:
In one embodiment of the primary cell according to the present invention, it is provided that the boron compound is a compound according to formula (8), where each of R1 to R3 independent from one another is a Cto Calkyl.
In one embodiment of the primary cell according to the present invention, it is provided that the compound according to formula (8) is 2,4,6-trimethoxyboroxine.
In one embodiment of the primary cell according to the present invention, it is provided that the boron compound is present in the electrolyte in a concentration in the range of 0.001 mol*lto 0.5 mol*l.
In one embodiment of the primary cell according to the present invention, it is provided that the alkali metal, serving as the active electrode material, is lithium, and the primary cell is a lithium battery.
In one embodiment of the primary cell according to the present invention, it is provided that the electrolyte is a non-aqueous electrolyte.
In one embodiment of the primary cell according to the present invention, it is provided that the non-aqueous electrolyte:
In one embodiment of the primary cell according to the present invention, it is provided that the electrolyte comprises an anhydrous alkali salt, in particular an anhydrous lithium salt, preferably LiClO, LiPF, LiBF, LiAsF, LiSbF, LiClO, LiAlCl, LiGaCl, LiC(SOCF), LiN(SOCF), LiSCN, LiOSCFCF, LiCFSO, LiOCF, LiSOF, LiB(CH), LiCFSOor a mixture thereof.
In one embodiment, the primary cell according to the present invention furthermore comprises a carbon monofluoride as the active electrode material, and particularly as the active cathode material. The carbon monofluoride may be present by itself or form hybrid cathodes with metal oxides, preferably of transition metals, for example MnO, SVO (silver oxide and vanadium pentoxide), copper silver vanadium oxide, cobalt oxide, nickel oxide, copper oxide, copper sulfide, iron sulfide, iron disulfide, titanium disulfide, or mixtures thereof.
In one embodiment, the primary cell according to the present invention comprises a cathode binder, in particular polytetrafluoroethylene, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyolefins, preferably thermoplastic elastomers, in particular ethylene propylene diene terpolymers, or mixtures thereof.
In one embodiment, the primary cell according to the present invention comprises carbon, in particular in the form of graphite, graphite powder or carbon black, or aluminum, in particular aluminum powder, titanium, in particular titanium powder, stainless steel, in particular stainless steel powder, or mixtures thereof, as a conducting additive.
According to claim, a boron compound is provided for use as an electrolyte additive of a primary cell comprising an alkali metal as the active electrode material, in particular an organic boron compound.
According to the present invention, it is particularly provided that the boron compound is a compound according to formula (1), (2), (3), (4), (7) or (8):
where each of R1, R2, R3, R4 and R5 independent from one another is selected from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl, thioether, heterocyclic compounds, aryl and heteroaryl, wherein R1, R2, R3, R4 or R5 is not thiophene.
In one embodiment of the use according to the present invention, it is provided that each of R1, R2, R3, R4 and R5 independent from one another is unsubstituted or is monosubstituted or multiple substituted with at least one substituent selected from the group consisting of: alkyl, fluoroalkyl, alkoxy, carbonyl, carboxyl, thiol, thio alkoxide, aryl, ether, thioether, nitro, cyano, amino, azido, amidino, hydrazino, hydrazono, carbamoyl, sulfo, sulfamoyl, sulfonylamino, alkylaminosulfate, alkylsulfonylamino and/or halogens, wherein R1, R2, R3, R4 or R5 is not thiophene.
In one embodiment of the use according to the present invention, it is provided that the boron compound is a compound according to formula (1), where R1 is an alkyl, in particular a Cto Calkyl, in particular methyl, cyclopropyl or cyclohexyl, or an aryl, in particular a phenyl, a benzyl or a naphthyl, which is unsubstituted or substituted with one or more Cto Calkyl, —F, —Cl, —Br, —I, —CN, —CFor —OCF, and each of R2 to R4 and R5 independent from one another is a CCalkyl.
In one embodiment of the use according to the present invention, it is provided that the is compound according to formula (1) is:
In one embodiment of the use according to the present invention, it is provided that the boron compound is a compound according to formula (2), where each of R1 to R4 and R5 independent from one another is a Cto Calkyl.
In one embodiment of the use according to the present invention, it is provided that the compound according to formula (2) is:
In one embodiment of the use according to the present invention, it is provided that the boron compound is a compound according to formula (3), where R1 is an alkyl, an alkenyl, in particular an allyl or an aryl, in particular a benzyl, phenyl, or benzoate, which is unsubstituted, or substituted with one or more Cto Calkyl, —F, —Cl, —Br, —I, —CN, —CFor —OCF, and each of R2 and R3 independent from one another is a Cto Calkyl.
In one embodiment of the use according to the present invention, it is provided that the compound according to formula (3) is:
In one embodiment of the use according to the present invention, it is provided that the boron compound is a compound according to formula (4), where each of R1, R2 and R3 independent from one another is a Cto Calkyl.
Unknown
May 19, 2026
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